Stabilizer combination

ABSTRACT

A description is given of novel stabilizer mixtures comprising at least one compound of the formula ##STR1## and at least one compound of the formula ##STR2## in which the variables are as defined in the claims. The novel stabilizer mixtures are suitable for stabilizing organic material, especially textile fibre materials, against damage by light, oxygen and heat.

The present invention relates to novel stabilizer mixtures comprisingmono- und bis-resorcinyltriazines, processes for their preparation, andtheir use for the photochemical and chemical stabilization of organicmaterial, preferably undyed or dyed textile fibre materials.

The invention provides stabilizer mixtures comprising at least onecompound of the formula ##STR3## and at least one compound of theformula ##STR4## in which R₁ und R₁ ' independently of one another areeach linear or branched C₁ -C₁₈ alkyl, C₃ -C₈ cycloalkyl, C₃ -C₆alkenyl, unsubstituted or substituted aryl or C₇ -C₁₂ aralkyl, R₂, R₂ ',R₃, R₃ ', R₄ and R₅ independently of one another are each hydrogen,unsubstituted or substituted, linear or branched C₁ -C₁₂ alkyl, orlinear or branched C₄ -C₂₈ alkyl, which is interrupted by one or more N,S or O atoms and which may be substituted further or are a radical--CO--R₆ or --SO₂ --R₆, and R₆ is C₁ -C₁₂ alkyl, unsubstituted or C₁ -C₄alkyl-substituted phenyl or C₇ -C₁₂ aralkyl.

R₁ and R₁ ' as C₁ -C₁₈ alkyl comprise straight-chain or branched alkylradicals, for example, methyl, ethyl, n- or isopropyl, n-, iso-, sec- ortert-butyl, 2-ethylbutyl, n- or isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1 -methylhexyl, n- or isoheptyl,1,1,3,3-tetra-methylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. R₁ and R₁ 'as alkyl, independently of one another, are each preferably C₁ -C₆alkyl, particularly preferably C₁ -C₄ alkyl, and with particularpreference are each methyl.

R₁ and R₁ ' as a cycloalkyl radical comprise, for example, a saturated3- to 8-membered carbocyclic ring, which is unsubstituted or substitutedby one or more C₁ -C₄ alkyl groups, preferably methyl groups. Examplesare cyclopentyl, cyclohexyl, methylcyclohexyl or cycloheptyl. As acycloalkyl radical, R₁ and R₁ ' are preferably and independently of oneanother each cyclohexyl which is unsubstituted or substituted by 1-3methyl groups.

Examples of suitable alkenyl radicals R₁ or R₁ ' are allyl, isopropenyl,2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl or3-methylbut-2-enyl. R₁ and R₁ ' as an alkenyl radical are, independentlyof one another, each preferably allyl or isopropenyl, and withparticular preference are each allyl.

R₁ and R₁ ' as an aryl radical are, for example, a biphenyl, naphthyl,or in particular, a phenyl radical, each of which can be substitutedfurther by, for example, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halogen.Preferred definitions of R₁ and R₁ ' as aryl radical are, independentlyof one another, each unsubstituted or C₁ -C₄ alkyl-substituted phenyl,and with particular preference are in each case phenyl.

Examples of suitable aralkyl radicals R₁ and R₁ ' are benzyl,α-methylbenzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl orphenylhexyl. R₁ and R₁ ' as an aralkyl radical, independently of oneanother, are each preferably benzyl or α-methylbenzyl, and withparticular preference are each benzyl.

The radicals R₁ and R₁ ' can be different or, preferably, identical.

A preferred embodiment of the present invention relates to stabilizermixtures comprising at least one of each compound of the above formulae(1) and (2) in which R₁ and R₁ ' independently of one another are eachC₁ -C₆ alkyl, cyclohexyl which is unsubstituted or substituted by 1-3methyl groups, or are allyl, isopropenyl, unsubstituted or C₁ -C₄alkyl-, C₁ -C₄ alkoxy- or halo-substituted phenyl, benzyl orα-methylbenzyl.

A particularly preferred embodiment of the present invention relates tostabilizer mixtures comprising at least one of each compound of theabove formulae (1) and (2) in which R₁ and R₁ ' are identical and areeach C₁ -C₄ alkyl, cyclohexyl, allyl, phenyl or benzyl.

An especially preferred embodiment of the present invention relates tostabilizer mixtures of compounds of the above formulae (1) and (2) inwhich R₁ and R₁ ' are identical and are each C₁ -C₄ alkyl, especiallymethyl.

Where R₂, R₂ ', R₃, R₃ ', R₄ or R₅ are C₁ -C₁₂ alkyl, this can, forexample, be one of the C₁ -C₁₂ alkyl radicals mentioned above for R₁ ora corresponding C₁ -C₁₂ alkyl radical which is substituted, for example,by halogen, cyano, hydroxyl, amino, C₁ -C₄ alkoxycarbonyl, carbamoyl,N-mono- or N,N-di-C₁ -C₄ alkyl carbamoyl, glycidyl or phenyl. Examplesof suitable C₁ -C₄ alkoxycarbonyl substituents are methoxycarbonyl orethoxycarbonyl. Glycidyl is the 2,3-epoxypropyl radical.

R₂, R₂ ', R₃, R₃ ', R₄ and R₅ as alkyl radical are, independently of oneanother, each preferably C₁ -C₆ alkyl, particularly preferably C₁ -C₄alkyl and with particular preference methyl, ethyl or n- or isopropyl.

Where R₂, R₂ ', R₃, R₃ ', R₄ or R₅ are an alkyl radical which isinterrupted by heteroatoms, then the radical is, for example,straight-chain or branched C₄ -C₂₈ alkyl, which is interrupted by one ormore groups --O--, --NH-- or --S-- and which may be substituted furtherby hydroxyl or by a radical --OR₆, in which R₆ is as defined above; insuch compounds, heteroatom groups --O--, --NH--or --S-- that are presentdo not occur adjacently. R₂, R₂ ', R₃, R₃ ', R₄ or R₅ as an alkylradical interrupted by heteroatoms are, preferably and independently ofone another, each a straight-chain or branched C₄ -C₂₈ alkyl radicalwhich is interrupted by one or more groups --O-- and is substituted byhydroxyl or by a radical --OR₆. R₂, R₂ ', R₃, R₃ ', R₄ and R₅ as aheteroalkyl radical are, independently of one another, each preferablyof the formula --(CH₂ CHR₇ --O)_(n) --R₈, in which R₇ is hydrogen,methyl or ethyl, R₈ is hydrogen, C₁ -C₁₂ alkyl or phenyl and n is aninteger from 1 to 9 , and with particular preference are of the formula--(CH₂ CHR₇ --O)_(n) --H, in which R₇ is methyl or, in particular,hydrogen and n is an integer from 1 to 9.

Where R₆ is a C₁ -C₁₂ alkyl radical it may be, for example, one of theC₁ -C₁₂ alkyl radicals mentioned above for R₁. R₆ as an alkyl radical ispreferably C₁ -C₄ alkyl, particularly preferably methyl or ethyl and,with special preference, methyl. Where R₆ is a phenyl radical, it ispreferably phenyl, o-, m- or p-tolyl and with particular preference,phenyl. Where R₆ is an aralkyl radical, it is preferably benzyl.

R₂, R₂ ', R₃, R₃ ', R₄ and R₅ are, independently of one another, eachpreferably hydrogen, C₁ -C₆ alkyl or straight-chain or branched C₄ -C₂₈alkyl, which is interrupted by one or more groups --O-- and issubstituted by hydroxyl or by a radical --OR₆, in which R₆ is C₁ -C₄alkyl, phenyl, o-, m- or p-tolyl or benzyl, or are unsubstituted or C₁-C₄ alkyl-substituted benzoyl or phenylsulfonyl. Particularly preferreddefinitions of R₂, R₂ ', R₃, R₃ ', R₄ and R₅ are, independently of oneanother, each hydrogen, C₁ -C₄ alkyl, a radical of formula --(CH₂ CHR₇--O)_(n) --H, in which R₇ is methyl or, in particular, hydrogen and n isan integer from 1 to 9, and benzoyl. R₂, R₂ ', R₃, R₃ ', R₄ and R₅,independently of one another, are with particular preference eachhydrogen, methyl, ethyl or n- or isopropyl.

A preferred embodiment of the present invention relates to thestabilizer mixtures comprising at least one of each compound of theabove formulae (1) and (2) in which R₂, R₂ ' and R₅ independently of oneanother are each C₁ -C₄ alkyl, a radical of the formula --(CH₂ CHR₇--O)_(n) --H, in which R₇ is methyl or, in particular, hydrogen and n isan integer from 1 to 9, or benzoyl, R₃ is hydrogen, C₁ -C₄ alkyl, aradical of the formula --(CH₂ CHR₇ --O)_(n) --H, in which R₇ is methylor, in particular, hydrogen and n is an integer from 1 to 9, or benzoyl,and R₃ ' and R₄ are each hydrogen.

A particularly preferred embodiment of the present invention relates tostabilizer mixtures comprising at least one of each compound of theabove formulae (1) and (2), in which R₂, R₂ ' and R₅ are identical andare each C₁ -C₄ alkyl, R₃ is hydrogen or C₁ -C₄ alkyl and R₃ ' and R₄are each hydrogen.

The compounds of the formula (1) are known, for example, from EP-A-0 584044 or can be prepared by the methods described therein, for example bycondensation of 1 mol-equivalent of cyanuric chloride with about 1mol-equivalent of a compound R₁ --SH, in which R₁ is as defined aboveand subsequent reaction of the condensation product with twomol-equivalents of the corresponding benzene compound in the presence ofa Lewis acid.

Some of the compounds of the formula (2) are novel. The inventionadditionally provides, therefore, compounds with the above formula (2),in which R₁ and R₁ ' independently of one another are each linear orbranched C₁ -C₁₈ alkyl, C₃ -C₈ cycloalkyl, C₃ -C₆ alkenyl or C₇ -C₁₂-aralkyl, R₄ and R₅ independently of one another are each hydrogen,unsubstituted or substituted, linear or branched C₁ -C₁₂ alkyl, linearor branched C₄ -C₂₈ alkyl which is interrupted by one or more N, S, or Oatoms and which may be substituted further, or are a radical --CO--R₆ or--SO₂ --R₆ and, R₆ is C₁ -C₁₂ alkyl, unsubstituted or C₁ -C₄alkyl-substituted phenyl or C₇ -C₁₂ aralkyl.

The compounds of the formula (2) can be prepared in an analogy to theknown compounds of the formula (1), for example by reacting 1mol-equivalent of cyanuric chloride with about 1 mol-equivalent of acompound R₁ --SH and about 1 mol-equivalent of a compound R₁ '--SH and,in a subsequent step, reacting the product with about 1 mol-equivalentof the corresponding benzene compound in the presence of a Lewis acid,preferably aluminium chloride, R₁ and R₁ ' each being as defined aboveand being different or, preferably, identical.

The novel stabilizer mixtures can be obtained by methods known per sefrom the individual compounds, for example by mixing them or subjectingthem to conjoint grinding or cocrystallization. It is also possible tocarry out mixing by simultaneous or successive incorporation of thecompounds of the formulae (1) and (2) into the textile fibre substratethat is to be stabilized.

The invention also provides the preparation of the novel stabilizermixtures by conjoint synthesis, which is particularly preferred forthose mixtures comprising at least one compound of the above formulae(1) and (2) in which R₁ and R₁ ' are identical. In accordance with thispreparation, the novel stabilizer mixtures are prepared, for example, by

(i) condensing a cyanuric halide, for example cyanuric fluoride orpreferably, cyanuric chloride, in aqueous or aqueous-organic solutionwith an excess of a compound of the formula

    R.sub.1 --S - X                                            (3)

in which X is hydrogen or a cation and R₁ is as defined above, in thepresence or absence of a hydrogen halide acceptor, which must be presentif X=hydrogen,

(ii) reacting the mixture obtainable in accordance with (i), comprisingthe compounds of the formulae ##STR5## with resorcinol in the presenceof a Lewis acid, and (iii) converting the mixture obtainable inaccordance with (ii), comprising the compounds of the formulae ##STR6##with or without one or more acylating or alkylating agents comprisingthe radicals R₂, R₂ ', R₃, R₃ ', R₄ and/or R₅, into a novel stabilizermixture.

The reaction of the compound of the formula (3) with the cyanuric halidein step (i) is known, for example, from GB-A-1,176,770, or can beperformed in analogy thereto. The reaction is conducted, for example, ata temperature of from -5° to 100° C. and, preferably, from 0° to 50° C.in a medium comprising water and, if desired, an organic solvent, forexample an akylbenzene such as toluene or xylene, a substituted benzenesuch as chlorobenzene, nitrobenzene or anisole, or an unsubstituted orsubstituted, aliphatic or cycloaliphatic hydrocarbon such as pentane,hexane, cyclohexane, dibutyl ether, methylene chloride or chloroform.Preferred organic solvents are alkylbenzenes, especially toluene, o-, m-or p-xylene or a mixture of different xylenes. Examples of suitablehydrogen halide acceptors in step (i) are the carbonates, bicarbonatesor hydroxides of alkali metals or of alkaline earth metals, andpreferably alkali metal hydroxides such as sodium or potassiumhydroxide. The addition of a hydrogen halide acceptor is unnecessary ifa compound of the formula (3a) is employed in which X is a cation, forexample an alkali metal, alkaline earth metal or ammonium cation, andpreferably an alkali metal cation such as the potassium or, inparticular, the sodium cation. The ratio in which the compounds of thefomulae (4a) and (4b) are obtained in step (i) depends, for example, onthe stoichiometric proportion of the reactants used, on the cyanurichalide and on the compound of the formula (3), and can vary, forexample, between 95 and 5% by weight of compound of the formula (4a) andbetween 5 and 95% by weight of compound of the formula (4b).

The reaction with resorcinol of the product obtainable in (i) takesplace generally under the customary conditions for Friedel-Craftsreactions, for example at a temperature of from 10° to 50° C. andpreferably, from 25° to 40° C. in the presence of a Lewis acid,advantageously aluminium chloride. In this reaction the resorcinol andthe Lewis acid are each advantageously present in at least equimolaramounts or, preferably, in a certain molar excess relative to the molaramount of the halogen which is to be replaced on the cyanuric halide.For example, both for the molar ratio of resorcinol/halogen to bereplaced, and for the molar ratio of Lewis acid/halogen to be replaced,a value which has been found favourable in each case is from 1:1 to 2:1and, preferably, from 1.1:1 to 1.5:1.

Steps (i) and (ii) of the novel process can be conducted separately orelse as a one-pot reaction. In the case of the preferred embodimentusing the one-pot procedure, the organic phase obtained in step (i) isadvantageously dried, for example by means of azeotropic distillation,and is reacted further, without additional purification, in accordancewith step (ii).

Examples of suitable alkylating agents in the optional step (iii) arealkyl halides R-Hal, in which R is any alkyl radical and Hal is halogen,for example chlorine, bromine or iodine, dialkyl carbonates, for exampledimethyl carbonate, mono- or dialkyl sulfates of the general formula

R--O--SO₂ --OH, R--O--SO₂ --O--R or R--O--SO₂ --C₆ H₅ --CH₃, alkylphosphonates of the formula R--O--P(O)(Z)--O--R, in which each R is anyalkyl radical and Z is, for example, C₁ -C₄ -alkyl or hydroxyl, or amideacetals, for example dimethylformamide dimethyl acetal. Examples ofmethylating agents are dimethyl sulfate, methyl tosylate or dimethylmethanephosphonate (DMMP). An ethyl radical R₂, R₂ ', R₃, R₃ ', R₄ or R₅is introduced, for example, using diethyl sulfate. The alkylationreaction is generally carried out at temperatures of, for example, from10° to 200° C. and, preferably, from 80° to 150° C., in the presence ofa base, for example an alkali metal carbonate or alkali metal hydroxide,examples being sodium carbonate, potassium carbonate or sodiumhydroxide, with an excess of alkylating agent, the degree of alkylationbeing influenced, for example, by the stoichiometry and the reactiontime. The hydroxyl groups present on the triazinyl ring, in the pposition relative to the bond, in the compounds of the formulae (5a) and(5b) are in general more readily accessible than those in the o positionand are therefore alkylated first. Examples of suitable acylating agentsare compounds of the formula R₆ --CO--Y or R₆ --SO₂ --Y in which R₆ isas defined above and Y is halogen, preferably chlorine.

A preferred stabilizer mixture obtained by the novel conjoint andsynthesis essentially comprises the compounds of the formula ##STR7## inwhich R₁ and R₂ are each subject to the definitions and preferencesindicated above. Particularly preferred stabilizer mixtures are thosecomprising from 50 to 95% by weight of compounds of the above formulae(1 a) and (1 b) and from 50 to 5% by weight of the compound of the aboveformula (2a).

Especially preferred stabilizer mixtures are those comprising from 50 to80% by weight of compounds of the above formulae (1 a) and (1 b) andfrom 50 to 20% by weight of the compounds of the above formula (2a) inwhich R₁ is C₁ -C₄ alkyl, cyclohexyl, allyl, phenyl or benzyl and R₂ isC₁ -C₄ alkyl, a radical of the formula --(CH₂ CHR₄ --O)_(n) --H, inwhich R₄ is methyl or in particular, hydrogen and n is an integer from 1to 9, or benzoyl.

The novel stabilizer mixtures can be used as a stabilizer for organicmaterials, especially against damage by light, oxygen or heat. The novelcompounds and stabilizer mixtures are very particularly suitable aslight stabilizers (UV absorbers).

Particular advantages of the novel mixtures include the outstandingresistance of the stabilized material to effects of weathering andlight, and the outstanding photostability of the incorporated stabilizermixtures. The excellent substrate compatibility of the novel mixtures isalso deserving of mention. The novel mixtures are notable in particularfor high affinity.

The materials to be stabilized can, for example, be oils, fats, waxes,cosmetics or biocides. Of particular interest is their use in polymericmaterials as present in plastics, rubbers, coating materials,photographic materials or adhesives. Examples of polymers and othersubstrates which can be stabilized in this way are the following:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, poly-but-1-ene, poly-4-methylpent-1-ene, polyisopreneor polybutadiene, as well as polymers of cycloolefins, for example ofcyclopentene or norbornene; furthermore polyethylene (which optionallycan be crosslinked), for example high-density polyethylene (HDPE),high-density and high molecular weight polyethylene (HDPE-HMW),high-density and ultrahigh molecular weight polyethylene (HDPE-UHMW),medium-density polyethylene (MDPE), low-density polyethylene (LDPE),linear low-density polyethylene (LLDPE), branched low-densitypolyethylene (BLDPE).

Polyolefins, i.e. polymers of monoolefins exemplified in the precedingparagraph, in particular polyethylene and polypropylene, can be preparedby different, and especially by the following, methods:

a) radical polymerization (normally under high pressure and at elevatedtemperature)

b) catalytic polymerization using a catalyst that normally contains oneor more metals of group IVb, Vb, VIb or VIII. These metals usually haveone or more ligands, such as oxides, halides, alcoholates, esters,ethers, amines, alkyls, alkenyls and/or aryls that may be either π- orσ-coordinated. These metal complexes may be in the free form or fixed onsubstrates, for example on activated magnesium chloride, titanium(IIII)chloride, alumina or silicon oxide. These catalysts may be soluble orinsoluble in the polymerization medium. The catalysts can be active assuch in the polymerization or further activators may be used, forexample metal alkyls, metal hydrides, metal alkyl halides, metal alkyloxides or metal alkyloxanes, the metals being elements of groups Ia, Iaand/or IIIa. The activators may be modified, for example, with furtherester, ether, amine or silyl ether groups. These catalyst systems areusually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ(DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene-propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene-but-1-ene copolymers,propylene-isobutylene copolymers, ethylene-but-1-ene copolymers,ethylene-hexene copolymers, ethylene-methylpentene copolymers,ethylene-heptene copolymers, ethylene-octene copolymers,propylene-butadiene copolymers, isobutylene-isoprene copolymers,ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylatecopolymers, ethylene-vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene-acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; and alsomixtures of such copolymers with one another and with polymers mentionedunder 1), for example polypropylene-ethylene-propylene copolymers,LDPE-ethylene-vinyl acetate copolymers, LDPE-ethylene-acrylic acidcopolymers, LLDPE-ethylene-vinyl acetate copolymers,LLDPE-ethylene-acrylic acid copolymers and alternating or randompolyalkylene-carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (e.g. tackifier resins) and mixtures ofpolyalkylenes and starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene-butadiene, styrene-acrylonitrile,styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate,styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride,styrene-acrylo-nitrile-methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene-propylene-diene terpolymer, and blockcopolymers of styrene such as styrene-butadiene-styrene,styrene-isoprene-styrene, styrene-ethylene-butylene-styrene orstyrene-ethylene-propylene-styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene, styrene andalkyl acrylates or alkyl methacrylates on polybutadiene, styrene andacrylonitrile on ethylene-propylene-diene terpolymers, styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate-butadiene copolymers, as well as mixturesthereof with the copolymers mentioned under 6), for example thecopolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubber, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride; as well as copolymersthereof such as vinyl chloride-vinylidene chloride, vinyl chloride-vinylacetate or vinylidene chloride-vinyl acetate.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates, polymethyl methacrylates,impact-modified with butyl acrylate, polyacrylamides andpolyacrylonitriles.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile-butadienecopolymers, acrylonitrile-alkyl acrylate copolymers,acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinylhalide copolymers or acrylonitrile-alkyl methacrylate-butadieneterpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, such as polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in point 1.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain comonomers, for example ethylene oxide; polyacetalsmodified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures thereof with styrenepolymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters and polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,such as polyamide 4, 6, 6/6, 6/10, 6/9, 6/12, 4/6, 12/12,11 and 12,aromatic polyamides starting from m-xylene, diamine and adipic acid;polyamides prepared from hexamethylenediamine and isophthalic and/orterephthalic acid and with or without an elastomer as modifier, forexample poly-2,4,4-trimethylhexamethylene terephthalamide orpoly-m-phenylene isophthalamide. Block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol. Also,polyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyether imides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and dialcohols and/orfrom hydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, aswell as block polyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

18a. Acid-modified polyesters.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, urea or melamine on the other hand, such as phenol-formaldehyderesins, urea-formaldehyde resins and melamine-formaldehyde resins.

22. Drying and nondrying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated di-carboxylic acids with polyhydric alcohols and alsovinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample from epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, for example products ofbisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, which arecrosslinked by means of customary curing agents such an anhydrides oramines, with or without accelerators.

27. Natural polymers such as cellulose, natural rubber, gelatin andderivatives thereof which have been chemically modified in apolymer-homologous manner, for example cellulose acetates, cellulosepropionates and cellulose butyrates, or the cellulose ethers such asmethyl cellulose; as well as rosins and derivatives.

28. Blends (polyblends) of the aforementioned polymers, for examplePP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PU,PC/thermoplastic PU, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

In addition to the novel mixture of compounds, the novel compositionsmay also comprise other stabilizers or other additives, such asantioxidants, other light stabilizers, metal deactivators, phosphites orphosphonites. Examples of these are the following stabilizers:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol,2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),4,4'-thiobis(6-tert-butyl-3-methylphenol),4,4'-thiobis(6-tert-butyl-2-methylphenol),4,4'-thiobis-(3,6-di-sec-amylphenol),4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol),2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis4-methyl-6-(α-methylcyclohexyl)-phenol!,2,2'-methylenebis(4-methyl-6-cyclohexylphenol),2,2'-methylenebis(6-nonyl-4-methylphenol),2,2'-methylenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(4,6-di-tert-butyl-phenol),2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis6-(α-methylbenzyl)-4-nonylphenol!, 2,2'-methylenebis6-(α,β-dimethylbenzyl)-4-nonylphenol!,4,4'-methylenebis(2,6-di-tert-butylphenol),4,4'-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl) butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis 3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate!,bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl!terephthalate,1,1 -bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. O--, N-- and S-benzyl compounds, for example3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis4-(1,1,3,3-tetramethylbutyl)phenyl!-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octyl mercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanu rate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

11 1. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylol-propane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo 2.2.2!octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo2.2.2!octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N, N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo 2.2.2!octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo2.2.2!octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazide, N,N'-bis2-(3- 3,5-di-tert-butyl-4-hydroxyphenyl!propionyloxy)ethyl!oxamide(Naugard®XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N'-di-isopropyl-p-phenylenediamine,N,N'-di-sec-butyl-p-phenylenediamine,N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N'-bis(1-methylheptyl)-p-phenylenediamine,N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine,N,N'-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N'-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,N-cyclo-hexyl-N'-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis(2-methylphenyl)amino!ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis 4-(1',3'-dimethylbutyl)phenyl!amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tertoctyldiphenylamines, a mixture of mono- anddialkylated nonyidiphenylamines, a mixture of mono- and dialkylateddodecyidiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butylltert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilisers

2.1.2-(2'-Hydroxyphenyl)benzotriazoles, for example2-(2'-hydroxy-5'-methylphenyl)-benzo-triazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-4'-octyloxyphenyl) benzotriazole,2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-2-(2-ethylhexyloxy)-carbonylethyl!-2'-hydroxyphenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-carbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-5'-2-(2-ethylhexyloxy)carbonylethyl!-2'-hydroxyphenyl)benzotriazole,2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2'-methylene-bis-4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol!; thetransesterification product of 2-3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl!-2H-benzotriazolewith polyethylene glycol 300; R--CH₂ CH₂ --COO--CH₂ CH₂ .brket open-st.₂where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl!benzotriazole;2-2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl!benzotriazole.

2.2.2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxyand 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-4-(1,1,3,3-tetramethylbutyl)phenol!, such as the 1:1 or 1:2 complex,with or without additional ligands such as n-butylamine, triethanolamineor N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickelsalts of the monoalkyl esters, e.g. the methyl or ethyl ester, of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes ofketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickelcomplexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or withoutadditional ligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxy-ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro4.5!decan-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N'-bis-(2,2,6,6-tetramethyl-4-piperi-dyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensateof2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro4.5!decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.136504-96-6!); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro 4,5!decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro 4,5!decaneund epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine, polymethylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)!siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide,N,N'-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl!-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2- 2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl!-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl!-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl!-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl!-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy!phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxamide,N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl) hydrazine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyldihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benzd,g!-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz d,g!-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-nitrilotriethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite!,2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-di-yl)phosphites:

Expecially preferred are the following phosphites:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl) phoshite, ##STR8## 5. Hydroxylamines, for example,N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine,N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhy-droxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhy-droxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zinkpyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (ionomers).

12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-4-(2-acetoxyethoxy)-phenyl!-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3- 4-(2-stearoyloxyethoxy)phenyl!benzofuran-2-one,3,3'-bis 5,7-di-tert-butyl-3-(4- 2-hydroxyethoxy!phenyl)benzofuran-2-one!, 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The novel stabilizer mixtures are especially suitable for thephotochemical and thermal stabilization of undyed, dyed or printedtextile fibre materials, which is also provided by the presentinvention. A corresponding process comprises treating the textile fibrematerial with a stabilizer mixture comprising at least one compound ofthe above formula (1) and at least one compound of the above formula(2).

Textile fibre materials suitable for treatment are primarily fibrematerials containing polyester or cellulose acetate. The term polyesterfibres should be understood as referring, for example, to celluloseester fibres, such as secondary cellulose acetate fibres and triacetatefibres, and especially linear polyester fibres which may have beenacid-modified, such fibres being obtained, for example, by condensationof terephthalic acid with ethylene glycol or of isophthalic acid orterephthalic acid with 1,4-bis(hydroxymethyl)cyclohexane, and alsofibres of copolymers of terephthalic and isophthalic acid with ethyleneglycol. Customary polyester fibres in the textile fibre industryconsist, in particular, of terephthalic acid and ethylene glycol.

The textile fibre material to be treated may also be a blend fabric ofpolyester fibres and other fibres, examples being blends ofpolyacrylonitrile/polyester, polyamide/polyester, polyester/cotton,polyester/viscose or polyester /wool fibres, which a reprinted or dyedin a customary, batch or continuous procedure.

The textile fibre material may be in a variety of made-up forms, forexample as piece goods such a knits or wovens, or as a yarn on, forexample, cheeses, warp beams, etc.

Also highly suitable for the novel process are textile fabrics in theapparel sector which are at least partially light-permeable. Where suchtextiles are treated in accordance with the novel process, it ispossible thereby to protect the skin tissue below the item of apparelagainst the damaging effect of UV radiation. This is manifested in thefact that textile fibre materials treated with a novel stabilizer orstabilizer mixture can have a sun protection factor (UPF=UltravioletProtection Factor) which is markedly increased relative to that ofuntreated fabric.

The UPF is defined as the ratio formed from a harmful dose of UVradiation without sun protection and a harmful dose of UV radiation withsun protection. Accordingly, a UPF is also a measure of the permeabilityof the untreated fibre materials and of the fibre materials treated witha novel compound or a novel mixture of compounds to UV radiation.Determining the UPF of textile fibre materials is explained, forexample, in WO 94/04515 or in J. Soc. Cosmet. Chem. 40, pages 127-133(1989) and can be carried out analogously.

The novel stabilizer mixtures are employed in an amount of, for example,from 0.01 to 10% by weight, preferably from 0.1 to 5 % by weight, basedon the weight on the fibre material.

The novel stabilizer mixtures are of low solubility in water and aretherefore applied in dispersed form. For this purpose they are ground toa fineness in accordance with the application conditions using, forexample, an appropriate dispersant and with the aid of, for example,quartz beads and a high-speed stirrer.

Examples of suitable dispersants for the stabilizer mixtures are:

acidic esters or their salts of alkylene oxide adducts, for exampleacidic esters or their salts of a polyadduct of from 4 to 40 mol ofethylene oxide with 1 mol of a phenol, or phosphoric esters of theadducts of from 6 to 30 mol of ethylene oxide with 1 mol of4-nonylphenol, 1 mol of dinonylphenol or, in particular, with 1 mol ofcompounds which are prepared by adding from 1 to 3 mol of substituted orunsubstituted styrenes onto 1 mol of phenol,

polystyrenesulfonates,

fatty acid taurides,

alkylated diphenyl oxide mono- or di-sulfonates,

sulfonates of polycarboxylic esters,

adducts of from 1 to 60, preferably 2 to 30 mol of ethylene oxide and/orpropylene oxide with fatty amines, fatty amides, fatty acids or fattyalcohols each having from 8 to 22 carbon atoms, or with trihydric tohexahydric alkanols of 3 to 6 carbon atoms, which adducts are convertedinto an acidic ester using an organic dicarboxylic acid or an inorganicpolybasic acid,

ligninsulfonates, and very especially

formaldehyde condensates, for examples condensates of ligninsulfonatesand/or phenol and formaldehyde, condensates of formaldehyde witharomatic sulfonic acids, such as condensates of ditolyl ether sulfonatesand formaldehyde, condensates of naphthalene sulfonic and/or naphthol-or naphthylamine sulfonic acids with formaldehyde, condensates ofphenolsulfonic acids and/or sulfonated dihydroxydiphenyl sulfone andphenols and/or cresols with formaldehyde and/or urea, and condensates ofdiphenyl oxide disulfonic acid derivatives with formaldehyde.

Where the textile fibre material to be stabilized is a dyed textilefibre material, as is preferred, then particularly suitable dyes aredisperse dyes of low solubility in water. Consequently, they are presentin the dyeing liquor mostly in the form of a fine dispersion. They maybelong to various dye classes, for example the acridone, azo,anthraquinone, coumarin, methine, perinone, naphthoquinoneimine,quinophthalone, styrene or nitro dyes. It is also possible in accordancewith the invention to employ mixtures of disperse dyes.

Dyeing takes place from an aqueous liquor by a continuous or batchprocedure. In the case of the batch procedure (exhaust procedure) theliquor ratio can be chosen within a wide range, for example from 1:1 to10:10, preferably from 1:6 to 1:50. The temperature at which dyeing iscarried out is at least 50° C. and generally not more than 140° C. It ispreferably within the range from 80° to 135° C.

In the case of continuous dyeing procedures the dyeing liquors, which inaddition to the dyes may include further auxiliaries, are applied to thepiece material by means, for example, of pad-mangling, spraying or knitpadding, and are developed using thermofix or HT steam processes.

Linear polyester fibres and cellulose fibres are preferably dyed by thehigh-temperature process in closed and pressure-resistant apparatus attemperatures >100° C., preferably between 110° and 135° C., and atatmospheric or superatmospheric pressures. Examples of suitable closedvessels are circulation apparatus, such as cheese or beam dyeingapparatus, winch becks, jet or drum dyeing machines, muff dyeingapparatus, paddles or jiggers.

Secondary cellulose acetate fibres are preferably dyed at temperaturesof 80°-85° C.

Where the novel stabilizer mixtures are employed in the dyeingapplication, then application is preferably such that, for example, thefibre material is first of all treated with these stabilizer mixturesand then dyeing is conducted, or, preferably, the fibre material istreated simultaneously with a stabilizer mixture and with the dye in thedyebath. However, the stabilizer mixtures can also be appliedsubsequently to the finished dyeing by means of thermofixing, forexample at from 190° to 230° C. within a period of from 30 seconds to 5minutes. It is also possible to pretreat textile material with a novelstabilizer mixture, in which case the textile material is dimensionallystabilized at the same time.

The dyeing liquors may also include further additives, examples beingdyeing assistants, dispersants, carriers, wool protectors, wettingagents and antifoams.

The dyebaths may additionally contain mineral acids, examples beingsulfuric acid or phosphoric acid, or, more expediently, organic acids,for example aliphatic carboxylic acids such as formic acid, acetic acid,oxalic acid or citric acid, and/or salts, such as ammonium acetate,ammonium sulfate or sodium acetate. The purpose of the acids inparticular is to establish the pH of the liquors used in accordance withthe invention, which is preferably between 4 and 5.

The bath, containing the dye, a stabilizer mixture and, if desired,further additives, and having been adjusted to a pH from 4.5 to 5.5, ispreferably entered initially with the fibre material, at from 40° to 80°C. for 5 minutes, and then the temperature is raised to 125-1 30° C.over the course of from 10 to 20 minutes and treatment is continued atthis temperature for from 15 to 90 minutes, preferably for 30 minutes.

The dyeings are finished by cooling the dyeing liquor to from 50° to 80°C., rinsing the dyeings with water, and, if desired, reduction-clearingthem in a customary manner in an alkaline medium. The dyeings are thenrinsed again and dried. Where vat dyes are used for the celluloseportion, the goods are customarily treated first of all withhydrosulfite at a pH of from 6 to 12.5 and then with an oxidizing agent,and finally are rinsed out.

For the preparation of prints, the novel stabilizer mixtures are addedin the form of their aqueous dispersions to the printing pastes. Theprinting paste comprises the appropriate stabilizer mixture in amountsof, for example, from 0.1 to 10%, preferably from 0.1 to 5%, based onthe weight of the printing paste.

The amount of dyes added to the printing pastes depends on the desiredshade; in general amounts of from 0.01 to 15 percent by weight,preferably from 0.02 to 10 percent by weight, based on the textilematerial employed, have been found to be appropriate.

In addition to the dyes and the aqueous stabilizer mixture dispersion,the printing pastes expediently comprise acid-stable thickeners,preferably of natural origin, such as cornflour derivatives, especiallysodium alginate on its own or as a mixture with modified cellulose, inparticular with preferably from 20 to 25 percent by weight ofcarboxymethylcellulose. In addition, the printing pastes may alsoinclude acid donors, such as butyrolactone or sodium hydrogen phosphate,preservatives, sequestering agents, emulsifiers, water-insolublesolvents, oxidizing agents or deaerating agents.

Particularly suitable preservatives are formaldehyde donors, such asparaformaldehyde or trioxane, especially aqueous formaldehyde solutionswith concentrations of from about 30 to 40 percent by weight; examplesof suitable sequestering agents are sodium nitrilotriacetate, sodiumethylenediaminetetraacetate, and especially sodium polymetaphosphate,especially sodium hexametaphosphate; particularly suitable emulsifiersare adducts of an alkylene oxide and a fatty alcohol, in particular anadduct of oleyl alcohol and ethylene oxide; suitable water-insolublesolvents are high-boiling saturated hydrocarbons, especially paraffinswith a boiling range of from about 160° to 210° C. (solvent naphthas);examples of suitable oxidizing agents are an aromatic nitro compound,especially an aromatic mono- or dinitrocarboxylic or -sulfonic acid,which may possibly be in the form of an alkylene oxide adduct, inparticular a nitrobenzenesulfonic acid; and examples of suitabledeaerating agents are high-boiling solvents, especially turpentine oils,higher alcohols, preferably C₈ - to C₁₀ alcohols, terpene alcohols ordeaerating agents based on mineral oils and/or silicone oils, especiallycommercial formulations of from about 15 to 25 percent by weight of amineral and silicone oil mixture and from about 75 to 85 percent byweight of a C₈ alcohol such as 2-ethyl-n-hexanol.

In the course of printing the fibre materials, the printing paste isapplied directly to the entire area, or sections, of the fibre material,advantageously using printing machines of customary construction, forexample inkjet printing, vigoureux printing, intaglio printing, rotaryscreen printing or planographic printing machines.

After printing, the fibre material is dried at temperatures up to 150°C., preferably from 80° to 120° C.

The material is then stabilized by heat treatment at temperatures ofpreferably from 100° to 220° C. Heat treatment is generally effectedunder pressure using superheated steam.

Depending on temperature, this stabilization may take from 20 seconds to10 minutes, preferably from 4 to 8 minutes.

The prints are finished likewise in a customary manner by rinsing withwater, and finishing can, if desired, be undertaken by additionalreduction clearing in an alkaline medium, for example using sodiumdithionite. In the latter case, the prints are again rinsed, dewateredand dried.

The textile fibres treated with the novel stabilizer mixtures exhibitgood resistance to the damaging effect of light, oxygen and heat. Inparticular, it is possible using the novel process to obtain highlylightfast and sublimation-resistant polyester dyeings and prints.Specific pretreatment or aftertreatment of the fibre material isunnecessary with the novel process.

In the Examples which follow the percentages are by weight. The amountsof the dyes and UV absorbers are based on pure substance.

EXAMPLE 1

984 g of ice are introduced with stirring into a mixture of 541.4 g ofcyanuric chloride in 1327 g of xylene (isomer mixture). Then, withthorough stirring, 1130 g of a 21 percent aqueous solution of sodiummethylmercaptide are run in over the course of 10 minutes, during whichthe internal temperature rises to about 30° C. Stirring is continued forone hour. After phase separation the lower, aqueous phase is separatedoff. The organic phase is washed once with 885 g of water, to give 2044g of a xylene solution which contains 18% by weight1-methylthio-3,5-dichloro-s-triazine and 7.1% by weight1,3-bis-methylthio-5-chloro-s-triazine.

EXAMPLE 2

63.71 g of anhydrous aluminium chloride are introduced at 25° C. andwith thorough stirring into 200 g of the xylene solution obtained inExample 1, containing 36 g of 1-methylthio-3,5-dichloro-s-triazine and14.2 g of 1,3-bis-methylthio-5-chloro-s-triazine. The mixture is stirredfor 15 minutes. Then a solution of 52.64 g of resorcinol in 110 g ofsulfolane is added dropwise to the reaction mixture over the course of1.5 h. During this time, the reaction temperature is raised from aninitial 45° C. to about 50° C. Finally, condensation is completed bystirring at 70°0 C. for 1.5 h more and then at 80° C. for one hour. Theemulsion-like mixture is cooled to 50° C. and the Friedel-Crafts complexis hydrolyzed by careful drop-wise addition of a mixture of 62 g of 32%hydrochloric acid and 455 g of water. The xylene is then removed byazeotropic distillation and the product suspension is filtered withsuction. The filter material is rinsed with hot water and dried underreduced pressure at 80° C., to give 78.1 g of a powder containing thecompounds of the formulae ##STR9## in a weight ratio A:B of 15:85.

EXAMPLE 3

60 ml of 2N sodium hydroxide solution are added dropwise to a suspensionof 20 g of the product mixture obtainable in Example 2 in 180 ml ofmethyl ethyl ketone. Then 13.99 g of dimethyl sulfate are added dropwiseto the mixture over the course of one hour at from 33° to 35° C. Themixture is subsequently stirred for 16 h and the product mixture isneutralized with 2N hydrochloric acid. The organic solvent is separatedoff by azeotropic distillation, and finally the crystalline products areseparated off by filtration. The filter residue is rinsed with water anddried under reduced pressure at 70° C., to give a powder containing thecompounds of the formulae C, D and E ##STR10## in a weight ratio of71:13:16.

EXAMPLE 4

The procedure described in Example 3 is repeated but using, instead of13.99 g of dimethyl sulfate, 17.88 g of diethyl sulfate and maintainingthe reaction temperature at 40° C.; this gives a product mixture whichessentially comprises the compounds of the formulae ##STR11##

EXAMPLE 5

15.4 g of sodium methyl mercaptide as a 21 percent aqueous solution areadded dropwise at 80° C. over the course of one hour to a toluenesolution of 28.7 g of 1-methylthio-3,5-dichloro-s-triazine (prepared asin GB-A-1,176,770, Example 1). Then 50 ml of water are added and themixture is subsequently stirred at 90°-95° C. for one hour more. Themixture is cooled to room temperature, and ice/ice-water and 100 ml of1N sodium hydroxide solution are added. After stirring for a short time,the organic phase is separated off, washed with water again and driedover calcium chloride. 14.7 g of anhydrous aluminium(lIl)chloride areintroduced into 121.5 g of the resulting toluene solution, containing17.1% by weight 1,3-bismethylthio-5-chloro-s-triazine. A solution of12.1 g of resorcinol and 25 ml of sulfolane is then added dropwise overthe course of 25 minutes at a temperature of from 45° to 50° C. Stirringis subsequently carried out at 75° C. for 3 h. The emulsion is cooled toabout 60° C. and the Friedel-Crafts complex is carefully decomposed witha mixture of 15 ml of conc. hydrochloric acid and 200 ml of water.Toluene is separated off by azeotropic distillation and the productsuspension is filtered with suction. The residue is washed thoroughlywith hot water and pressed. The crude product is recrystallized fromwater/dioxane to give the compound of the formula ##STR12## as a powder.

EXAMPLE 6

3.37 g of sodium carbonate are added to a suspension of 8.43 g of thecompound of Example 5 in 27.9 g of dimethyl methylphosphonate, and themixture is heated at 120° C. for23/4 h. The reaction mixture is cooledto 75°-80° C., and a mixture of 70 ml of methanol and 20 ml of water isadded dropwise. After cooling to room temperature, the solid precipitateis filtered off with suction, then washed with a little methanol and,finally, washed thoroughly with hot water. It is dried under reducedpressure at 70° C. and is purified by recrystallization from petroleumether/dioxane, to give the compound of the formula ##STR13## as a whitepowder.

EXAMPLE 7

250 g of ice are introduced with stirring into a mixture of 92.2 g ofcyanuric chloride in 400 ml of toluene. Subsequently a solution of 61.9g of sodium ethanethiolate in 250 ml of water is added dropwise withthorough stirring over the course of about 1.5 h, during which theinternal temperature rises gradually to about 30° C. Stirring iscontinued at about 48° C. for 15 minutes more, and the mixture is leftto cool. Following phase separation, the aqueous phase is separated offand the organic phase is washed three times with 500 ml portions ofwater, to give, after drying over calcium chloride, 590.9 g of a toluenesolution containing 11.5% by weight of 1-ethylthio-3,5-dichloro-s-triazine and 3.48% by weight of1,3-bisethylthio-5-chloro-s-triazine.

EXAMPLE 8

95.8 g of anhydrous aluminium(III) chloride are introduced with thoroughstirring at room temperature into 564.5 g of the toluene solution fromExample 7, and with gentle heating a red solution forms. Heating iscontinued to 40° C., and a solution of 79.2 g of resorcinol in 165 ml ofsulfolane is added dropwise over the course of 1.5 h. During this timethe internal temperature rises to 57° C. The emulsion is subsequentlystirred at 80° C. for 4 h. The reaction mass, cooled to about 50° C., isdischarged onto 1000 g of ice/250 ml of water. Toluene is subsequentlyremoved by azeotropic distillation, and the aqueous product suspensionis filtered. The residue is washed thoroughly with hot and cold wateruntil it gives a neutral reaction to congo. Drying under reducedpressure at 80° C. gives 133.7 g of a bright yellow powder containingthe compounds of the formulae ##STR14## in a weight ratio A':B' of24:76.

EXAMPLE 9

91.8 ml of 2N sodium hydroxide solution are introduced dropwise into amixture of 20 g of the product from Example 8 in 100 ml of water, duringwhich the temperature is held at 20° C. Then 18.5 g of dimethyl sulfateare introduced dropwise over the course of 1.5 h, during which the pH ofthe reaction mixture is kept constant at 11 by simultaneous dropwiseaddition of 2N sodium hydroxide solution. The mixture is subsequentlystirred at room temperature for 21 h and filtered. The residue issuspended again in water and neutralized with dilute hydrochloric acid.After refiltration, the residue is washed thoroughly with water anddried under reduced pressure at 70° C., to give a beige powdercontaining the compounds of the fomulae ##STR15## in a weight ratioC':D' of 22:78. Dyeing Examples:

(i) Preparing a stabilizer formulation:

10 g of the stabilizer mixture obtained in Example 3, 20 ml of a 10%aqueous solution of the triethanolamine salt oftristyrylphenyl-polyethylene glycol-phosphoric acid and 25 g of quartzbeads (1 mm in diameter) are placed in a high-speed stirrer and areground for 16 hours. The ground material is then passed through afine-meshed sieve to remove the glass beads, 0.5 g of xanthan gum (e.g.Biopolymer®AG) is added with stirring, and the formulation is adjustedwith water to a stabilizer content of 10% by weight. The fineness of thedispersion is about 0.5-2 μm.

(ii) Use in exhaust dyeing::

A 10 g sample of a polyester tricot is dyed in an HT dyeing machine(e.g. Turbomat® from Mathis, Niederhasli) at a liquor ratio of 10:1. Theaqueous dyeing liquor contains 2 g/l ammonium sulfate, 0.5 g/l dyeingassistant (Univadin® 3-flex), 0.5% by weight, based on the polyestertricot, of the UV absorber formulation prepared in (i), and 0.89% byweight, based on the polyester tricot, of a dye mixture comprising

18.5% by weight of dye F₁ of the formula ##STR16## 18.5% by weight ofdye F₂ of the formula ##STR17## 17.4% by weight of dye F₃ of the formula##STR18## 11.6% by weight of dye F₄ of the formula ##STR19## 14.3% byweight of dye F₅ of the formula ##STR20## 10.2% by weight of dye F₆ ofthe formula ##STR21## 9.5% by weight of dye F₇ of the formula ##STR22##

The dyeing liquor is adjusted with acetic acid to a pH of 5, homogenizedand placed together with the tricot in a pressure dyeing pot. Dyeing isbegun at 70° C., and then the contents are heated to 100° C. over thecourse of 10 minutes and to 130° C. over the course of a further 20minutes. After a dyeing time of 30 minutes at this temperature, thecontents are cooled to 50° C. and the dyed fabric is given a hot andcold rinse and reduction-cleaned at 70° C. with a liquor containing 3ml/l of 30% sodium hydroxide solution and 2 g/l of sodium dithionite.Rinsing and drying give a polyester tricot which is dyed grey-violet andhas very good hot light fastness.

(iii) If the procedure described under (ii) is repeated but thepolyester tricot is dyed with a dyeing liquor which does not contain thestabilizer formulation prepared in (i), the hot light fastness of theresulting dyeing is markedly lower.

(iv) If the procedure described under (ii) is repeated but dyeing iscarried out with a dyeing liquor which contains 1.15% by weight, basedon the polyester tricot, of a dye mixture comprising 13% by weight eachof dyes F₁ and F₂, 38.1% by weight of dye F₃, 25.4% by weight of dye F₄,4.4% by weight of dye F₅, 3.2% by weight of dye F₆ and 2.9% by weight ofdye F₇, a polyester tricot is obtained which is dyed wine-red and hasvery good hot light fastness.

(v) If the procedure described under (iv) is repeated but the polyestertricot is dyed with a dyeing liquor which does not contain thestabilizer formulation prepared in (i), a dyeing with a much lower hotlight fastness is obtained.

Printing Example: For printing polyester textured tricot, a printingpaste is prepared from a stock thickener, dyes and a stabilizer mixture.

The composition of the stock thickener is as follows:

    ______________________________________           120 g Starch ether thickener           480 g Sodium alginate thickener           5 g   Sodium hydrogen phopshate           5 g   Printing assistant           5 g   Sodium chlorate           385 g Deionized water           1000 g                 Stock thickener    ______________________________________

The printing paste has the following composition:

3.6 g of dye F₂ as in the Dyeing Example

3.4 g of a dye mixture comprising the dye F₃ as in the Dyeing Exampleand the dye of the formula ##STR23##

0.4 g of dye F₇ as in the Dyeing Example

1.6 g of dye F₆ as in the Dyeing Example

60 g of a stabilizer mixture according to Example 3, as a 20% groundformulation

931 g of stock thickener.

This printing paste is used to print cleaned pieces of polyester tricoton a printing table. The samples are then dried at 100° C. for 10minutes and subsequently steamed with superheated steam at 1 80° C. for8 minutes. The printed fabric is given hot and cold rinses and isreduction-cleared at 70° C. using a liquor containing 2 ml/l 30% sodiumhydroxide solution and 3 g/l sodium dithionite. Rinsing and drying givea polyester tricot with a reddish beige print which has very good hotlight fastness.

If the procedure described above is repeated but using a printing pastewhich does not contain the stabilizer formulation, a dyeing is obtainedwhich has markedly lower hot light fastness.

What is claimed is:
 1. A stabilizer mixture comprising at least onecompound of the formula ##STR24## and at least one compund of theformula ##STR25## in which R₁ and R₁ ' independently of one another areeach linear or branched C₁ -C₁₈ alkyl, C₃ -C₈ cycloalkyl, C₃ -C₆alkenyl, unsubstituted or C₁ -C₄ alkyl-, C₁ -C₄ alkoxy- orhalo-substituted biphenyl, unsubstituted or C₁ -C₄ alkyl-, C₁ -C₄alkoxy- or halo-substituted naphthyl, unsubstituted or C₁ -C₄ alkyl-, C₁-C₄ alkoxy- or halo-substituted phenyl or C₇ -C₁₂ aralkyl, R₂, R₂ ', R₃,R₃ ', R₄ and R₅ independently of one another are each hydrogen,unsubstituted or halo-, cyano-, hydroxyl-, amino-, C₁ -C₄alkoxycarbonyl-, carbamoyl, N-mono- or N,N-di-C₁ -C₄ alkyl carbamoyl-,glycidyl or phenyl-substituted linear or branched C₁ -C₁₂ alkyl, orlinear or branched C₄ -C₂₈ alkyl, which is interrupted by one or more N,S or O atoms and which is unsubstituted or substituted by hydroxyl or bya radical --OR₆ or are a radical --CO--R₆ or --SO₂ --R₆, and R₆ is C₁-C₁₂ alkyl, unsubstituted or C₁ -C₄ alkyl-substituted phenyl or C₇ -C₁₂aralkyl.
 2. A stabilizer mixture according to claim 1, wherein R₁ and R₁' independently of one another are each C₁ -C₆ alkyl, cyclohexyl whichis unsubstituted or substituted by 1-3 methyl groups, allyl,isopropenyl, unsubstituted or C₁ -C₄ alkyl-, C₁ -C₄ alkoxy orhalo-substituted phenyl, benzyl or α-methylbenzyl.
 3. A stabilizermixture according to claim 1, wherein R₁ and R₁ ' are identical and areeach C₁ -C₄ alkyl, cyclohexyl, allyl, phenyl or benzyl.
 4. A stabilizermixture according to claim 1, wherein R₁ and R₁ ' are identical and areeach methyl.
 5. A stabilizer mixture according to claim 1, wherein R₂,R₂ ', R₃, R₃ ', R₄ and R₅ independently of one another are eachhydrogen, C₁ -C₆ alkyl or straight-chain or branched C₄ -C₂₈ alkyl whichis interrupted by one or more groups --O-- and is substituted byhydroxyl or by a radical --OR₆, in which R₆ is C₁ -C₄ alkyl, phenyl, o-,m- or p-tolyl or benzyl, or are u nsubstituted or C₁ -C₄alkyl-substituted benzoyl or phenylsulfonyl.
 6. A stabilizer mixtureaccording to claim 1, wherein R₂, R₂ ', R₃, R₃ ', R₄ and R₅independently of one another are each hydrogen, C₁ -C₄ alkyl, a radicalof the formula --(CH₂ CHR₇ --O)_(n) --H, in which R₇ is methyl orhydrogen and n is an integer from 1 to 9, or are benzoyl.
 7. Astabilizer mixture according to claim 1, wherein R₂, R₂ ' and R₅independently of one another are each C₁ -C₄ alkyl, a radical of theformula --(CH₂ CHR₇ --O)_(n) --H, in which R₇ is methyl or hydrogen andn is an integer from 1 to 9, or are benzoyl, R₃ is hydrogen, C₁ -C₄alkyl, a radical of the formula --(CH₂ CHR₇ --O)_(n) --H, in which R₇ ismethyl or hydrogen and n is an integer from 1 to 9, or is benzoyl, andR₃ ' and R₄ are each hydrogen.
 8. A stabilizer mixture according toclaim 1 wherein R₂, R₂ ' and R₅ are identical and are each C₁ -C₄ alkyl,R₃ is hydrogen or C₁ -C₄ alkyl and R₃ ' and R₄ are each hydrogen.
 9. Astabilizer mixture according to claim 1 comprising essentially thecompounds of the formula ##STR26## in which R₁ is linear or branched C₁-C₁₈ alkyl, C₃ -C₈ cycloalkyl, C₃ -C₆ alkenyl, unsubstituted orsubstituted aryl or C₇ -C₁₂ aralkyl, and R₂ is hydrogen, unsubstitutedor substituted linear or branched C₁ -C₁₂ alkyl, or linear or branchedC₄ -C₂₈ alkyl which is interrupted by one or more N, S or O atoms andwhich may be substituted further or are a radical --CO--R₆ or --SO₂--R₆, and R₆ is C₁ -C₁₂ alkyl, unsubstituted or C.sub. -C₄alkyl-substituted phenyl or C₇ -C₁₂ aralkyl.
 10. A stabilizer mixtureaccording to claim 9, comprising from 50 to 95% by weight of compoundsof the formulae (1a) and (1b) and from 50 to 5% by weight of thecompound of the formula (2a).
 11. A stabilizer mixture according toclaim 9, comprising from 50 to 80% by weight of compounds of theformulae (1a) and (1b) and from 50 to 20% by weight of the compound ofthe formula (2a), in which R₁ C₁ -C₄ alkyl, cyclohexyl, allyl, phenyl orbenzyl and R₂ is C₁ -C₄ alkyl, a radical of the formula --(CH₂ CHR₄--O)_(n) --H, in which R₄ is methyl or hydrogen and n is an integer from1 to 9, or are benzoyl.